KR20250011919A - Composition for carbon-doped silicon-containing film and method of using same - Google Patents

Abstract

Compositions and methods of using the compositions in the fabrication of electronic devices are disclosed. Compounds, compositions, and methods for depositing low dielectric constant (<4.0) and high oxygen ash resistance silicon-containing films, such as, without limitation, carbon-doped silicon oxide, are disclosed.

Description

Composition for carbon-doped silicon-containing film and method of using same

Cross-reference to related applications

This application claims the benefit of U.S. Provisional Patent Application Serial No. 63/341,635, filed May 13, 2022.

Technical field

Compositions and methods for fabricating electronic devices are described herein. More specifically, compounds for depositing low dielectric constant (<4.0) and high oxygen ash resistance silicon-containing films, such as, without limitation, carbon-doped silicon oxide, carbon-doped silicon nitride, and carbon-doped silicon oxynitride, and compositions and methods comprising the same are described herein.

There is a need in the art to provide compositions and methods of using same for depositing silicon-containing films doped with high carbon content (e.g., greater than about 10 atomic % carbon as measured by X-ray photoelectron spectroscopy (XPS)) for certain applications within the electronics industry.

U.S. Patent No. 8,575,033 describes a method for depositing a silicon carbide film on a substrate surface. The method involves the use of a vapor phase carbosilane precursor and may utilize a plasma enhanced atomic layer deposition process.

U.S. Publication No. 2013/022496 A teaches a method for forming a dielectric film having Si-C bonds on a semiconductor substrate by atomic layer deposition (ALD), the method comprising the steps of: (i) adsorbing a precursor on a surface of the substrate; (ii) reacting the precursor adsorbed on the surface with a reactant gas; and (iii) repeating steps (i) and (ii) to form a dielectric film having at least Si-C bonds on the substrate.

PCT Publication No. WO14134476 A1 describes a method for depositing a film comprising SiCN and SiOCN. Certain methods include the step of exposing a substrate surface to first and second precursors, wherein the first precursor has the formula (X _y H _3-y Si)zCH _4-z , (X _y H _3-y Si)(CH ₂ )(SiX _p H _2-p )(CH ₂ )(SiX _y H _3-y ), or (X _y H _3-y Si)(CH ₂ ) _n (SiX _y H _3-y ), wherein X is a halogen, y has a value from 1 to 3, z has a value from 1 to 3, p has a value from 0 to 2, and n has a value from 2 to 5, and wherein the second precursor comprises a reduced amine. Certain methods also include the step of exposing the substrate surface to an oxygen source to provide a film comprising carbon-doped silicon oxide.

The document [Hirose, Y., Mizuno, K., Mizuno, N., Okubo, S., Okubo, S., Yanagida, K. and Yanagita, K. (2014)) "Method of manufacturing semiconductor device, substrate processing apparatus, and recording medium" (U.S. Publication No. 2014/287596 A)] describes a method of manufacturing a semiconductor device, comprising a step of forming a thin film containing silicon, oxygen, and carbon on a substrate by performing a cycle a predetermined number of times, wherein the cycle includes supplying a precursor gas containing silicon, carbon, and a halogen element and having a Si-C bond, and a first catalyst gas to the substrate; and supplying an oxidizing gas and a second catalyst gas to the substrate.

The literature [Hirose, Y., Mizuno, N., Yanagita, K. and Okubo, S. (2014)) "Method of manufacturing semiconductor device, substrate processing apparatus, and recording medium." (U.S. Patent No. 9,343,290 B)] describes a method of manufacturing a semiconductor device, the method including a step of forming an oxide film on a substrate by performing a cycle a predetermined number of times. The cycle includes: supplying a precursor gas to the substrate; and supplying ozone gas to the substrate. When supplying the precursor gas, the precursor gas is supplied to the substrate in a state where a catalyst gas is not supplied to the substrate, and when supplying the ozone gas, the ozone gas is supplied to the substrate in a state where an amine-based catalyst gas is supplied to the substrate.

U.S. Patent No. 9,349,586 B discloses a thin film having desirable etch resistance and low dielectric constant.

U.S. Publication No. 2015/0044881 A describes a method for forming a film containing carbon added at a high concentration and formed with high controllability. The method for manufacturing a semiconductor device comprises the step of performing a cycle a predetermined number of times to form a film containing silicon, carbon, and a predetermined element on a substrate. The predetermined element is one of nitrogen and oxygen. The cycle comprises supplying a precursor gas containing at least two silicon atoms, carbon, and a halogen element per mole and having a Si-C bond to the substrate, and supplying a modifying gas containing the predetermined element to the substrate.

A reference entitled ["Highly Stable Ultrathin Carbosiloxane Films by Molecular Layer Deposition", Han, Z. et al., Journal of Physical Chemistry C, 2013, 117, 19967] teaches the growth of carbosiloxane films using 1,2-bis[(dimethylamino)dimethylsilyl]ethane and ozone. Thermal stability indicates that the films show little thickness loss at 60°C and are stable up to 40°C.

The literature [Liu et al, Jpn. J. Appl. Phys., 1999, Vol. 38, 3482-3486] teaches the use of H ₂ plasma on polysilsesquioxanes deposited by spin-on technology. H ₂ plasma provides stable dielectric constant and improves film thermal stability and O ₂ ash (plasma) treatment.

The literature [Kim et al, Journal of the Korean Physical Society, 2002, Vol. 40, 94] teaches that H ₂ plasma treatment on PECVD carbon-doped silicon oxide films improves the leakage current density (by a factor of 4-5) while increasing the dielectric constant from 2.2 to 2.5. The carbon-doped silicon oxide films after H ₂ plasma are less damaged during the oxygen ashing process.

The literature [Posseme et al, Solid State Phenomena, 2005, Vol. 103-104, 337] teaches different H ₂ / inert plasma treatments on carbon-doped silicon oxide PECVD films. No improvement in k was observed after H ₂ plasma treatment, suggesting no bulk modification.

There is a need to develop liquid compositions for chlorosilane precursors, such as 1,1,3,3-tetrachloro-1,3-disilacyclobutane, suitable for vapor delivery methods for ALD applications. The compositions must meet certain important requirements for successful commercialization, including: the solvent must not react with the chlorosilane; the chlorosilane chemical must have high solubility in the solvent; the chlorosilane must not precipitate or phase separate during transport when exposed to low temperatures; the solvent must be capable of being manufactured with high purity and dried to low moisture content; the formulated solution must have an acceptable viscosity; and the vapor pressure of the solvent must be similar to the vapor pressure of the chlorosilane chemical.

The compositions described herein satisfy these criteria. The compositions and methods described herein overcome the problems of the prior art by providing compositions or formulations for depositing conformal silicon-containing films having one or more of the following properties: i) a dielectric constant less than 4.0; ii) an etch rate (e.g., 0.22 Å/s in 1:99 diluted HF) that is at most 0.5 times the etch rate of thermal silicon oxide as measured in diluted hydrofluoric acid (e.g., 0.45 Å/s in 1:99 diluted HF) and a carbon content of at least about 10 atomic weight percent (at. %) as measured by x-ray emission spectroscopy (XPS); ii) oxygen ash resistance, i.e., the susceptibility of the dielectric constant of the film to a decrease in diluted HF (dHF) due to subjecting the film to an oxygen ashing process or exposing the film to an oxygen plasma and the wet etch rate of the film; and (iv) less than 2.0 at. %, preferably less than 1.0 at. %, most preferably less than 0.5 at. % chlorine impurities in the resulting film. The oxygen ash resistance can be quantified by the damage thickness of the film after the O ₂ ashing process as measured by a dHF dip (e.g., a damage thickness of < 50 Å). The oxygen ash resistance is also exemplary when the film dielectric constant after the O ₂ ashing process remains less than 4.0. Desirable properties that can be achieved by the present invention are further illustrated in the Examples below.

In one particular embodiment, the compositions described herein can be used in a method of depositing carbon-doped silicon oxide films using thermal atomic layer deposition (ALD).

In one aspect, a composition for depositing a silicon-containing film is disclosed, the composition comprising: (a) 1,1,3,3-tetrachloro-1,3-disilacyclobutane; and (b) a solvent selected from the group consisting of mesitylene (b.p. 165°C), 2-methyl-nonane (b.p. 167°C), 1,2,4,5-tetramethylpiperazine (b.p. 166°C), ethoxy-benzene (b.p. 171°C), and 1-ethyl-4-methyl-benzene (b.p. 162°C).

In one aspect, a composition for depositing a silicon-containing film is disclosed, comprising: (a) 1,1,3,3-tetrachloro-1,3-disilacyclobutane; and (b) mesitylene.

In another aspect, a method of forming a carbon-doped silicon nitride film having a carbon content in the range of 15 at. % to 30 at. % via a thermal ALD process, comprising the steps of: a) disposing one or more substrates comprising surface features into a reactor; b) heating the reactor to one or more temperatures in the range of ambient temperature to about 550° C. and optionally maintaining the reactor at a pressure of less than or equal to 100 torr; c) introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene into the reactor; d) purging with an inert gas; e) providing a nitrogen source to the reactor to react with the 1,1,3,3-tetrachloro-1,3-disilacyclobutane to form the carbon-doped silicon nitride film; f) purging with an inert gas to remove reaction byproducts; g) repeating steps c through f to provide a desired thickness of the carbon-doped silicon nitride film. h) treating the formed carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from about ambient temperature to about 1000° C., or from about 100° C. to about 400° C. according to one embodiment to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film; and exposing the carbon-doped silicon oxide film to a plasma comprising hydrogen. A method of forming a carbon-doped silicon oxide film having a carbon content in the range of 15 at. % to 30 at. % is disclosed.

In another aspect, a method of forming a carbon-doped silicon oxide film having a carbon content in the range of 15 at. % to 30 at. % via a thermal ALD process, comprising: a) disposing one or more substrates comprising surface features in a reactor; b) heating the reactor to one or more temperatures in the range of ambient temperature to about 150° C. and optionally maintaining the reactor at a pressure of less than or equal to 100 torr; c) introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane, mesitylene, and a catalyst into the reactor; d) purging the reactor with an inert gas; e) providing water vapor to the reactor to react with the 1,1,3,3-tetrachloro-1,3-disilacyclobutane in the presence of the catalyst to form the carbon-doped silicon oxide film; And f) purging the reactor with an inert gas to remove any reaction byproducts, and repeating steps c) to f) to provide a desired thickness of the carbon-doped silicon oxide film. A method of forming a carbon-doped silicon oxide film having a carbon content in the range of 15 at. % to 30 at. % is disclosed.

In another aspect, a stainless steel container containing the invention composition is disclosed.

The embodiments of the present invention may be used alone or in various combinations with each other.

Figure 1 illustrates an overlay of the vapor pressure curves of 1,1,3,3-tetrachloro-1,3-disilacyclo-butane and mesitylene;
FIG. 2 illustrates the concentration of a 20 wt % solution of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene as a function of the percentage of material used in the vessel during the vapor withdrawal transfer process; the square symbols represent the concentration profile when the vessel was maintained at 70° C.; the circular symbols represent the concentration profile when the vessel was maintained at 80° C.
Figure 3 illustrates the concentration of common stainless steel metals and the plot shows the analysis of a 20 wt% solution of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene stored in a stainless steel commercial container;
Figure 4 illustrates the cycle-wise growth (GPC) of a film deposition using a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane among mesitylenes.

Described herein are compositions and methods for depositing silicon-containing films that are carbon-doped (e.g., having a carbon content of greater than or equal to about 10 at. % as measured by XPS) via a deposition process, such as, without limitation, a thermal atomic layer deposition process. Films deposited using the compositions and methods described herein exhibit very low etch rates, such as an etch rate that is at least 0.5 times lower than thermal silicon oxide as measured in diluted hydrofluoric acid (e.g., about 0.22 Å/s or less, or about 0.15 Å/s or less in diluted HF (0.5 wt %, i.e., 1:99 diluted HF)), or an etch rate that is at most 0.1 times the etch rate of thermal silicon oxide (0.15 Å/s), or an etch rate that is at most 0.05 times the etch rate of thermal silicon oxide (0.02 Å/s), or an etch rate that is at most 0.01 times the etch rate of thermal silicon oxide), and exhibit other tunable properties, such as, but not limited to, variability in density, dielectric constant, refractive index, and elemental composition.

In certain embodiments, the silicon precursors, and methods of using same, described herein impart one or more of the following characteristics in the following manner. First, an as-deposited, reactive carbon-doped silicon nitride film is formed using a silicon precursor comprising two Si-C-Si bonds, and a nitrogen source. Without wishing to be bound by any theory or explanation, it is believed that some of the Si-C-Si bonds from the silicon precursor remain in the resulting as-deposited film and provide a high carbon content of at least 10 at. % or greater as measured by XPS (e.g., about 20 to about 30 at. %, about 10 to about 20 at. %, and in some cases, about 10 to about 15 at. % carbon). Secondly, when the immediately post-deposited film is intermittently exposed to an oxygen source such as water during the deposition process, as a post-deposition treatment, or a combination thereof, at least a portion or all of the nitrogen content in the film is converted to oxygen, thereby providing a film selected from a carbon-doped silicon oxide or carbon-doped silicon oxynitride film. The nitrogen in the immediately post-deposited film is released as one or more nitrogen-containing byproducts, such as ammonia or amine groups.

In this or other embodiments, the final film is porous and has a density of less than or equal to about 1.7 grams per cubic centimeter (g/cc) and an etch rate of less than or equal to 0.20 Å/s in 0.5 wt % diluted hydrogen fluoride.

In one embodiment, a composition for depositing a silicon-containing film comprises (a) 1,1,3,3-tetrachloro-1,3-disilacyclobutane; and (B) mesitylene. In some embodiments, the composition can be delivered via direct liquid injection into a reactor chamber for the silicon-containing film using conventional direct liquid injection equipment and methods. The concentration of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in the solvent can range from 1 to 90 wt %, preferably from 10 to 80 wt %, and most preferably from 15 to 60 wt %, depending on the solvent selected.

Mesitylene is the optimal solvent for the composition because it has a normal boiling point very similar to that of 1,1,3,3-tetrachloro-1,3-disilacyclobutane (165°C and 167°C, respectively). The two components of the composition have similar boiling points and similar vapor pressure curves over the temperature range of interest. The similarity in volatility of the chlorosilane chemical and the solvent ensures that the composition of the vapor stream and the composition of the liquid blended product remain constant as the blended product is depleted during vapor transport. This consistency of the liquid and vapor compositions of the blended product is important to ensure a reliable, robust deposition process. Mesitylene is also hydrophobic and therefore can be readily dried by practically known methods, such as treatment with molecular sieves, to produce a solvent having less than 10 ppm water, or preferably less than 5 ppm water. Achieving these low water levels is most important as this will minimize the amount of acidic byproducts such as HCl formed when chlorosilanes such as 1,1,3,3-tetrachloro-1,3-disilacyclobutane are dissolved in the solvent. Eliminating or reducing trace amounts of HCl in the final blended product is critical to achieving a compounded product that is compatible with common container construction materials such as stainless steel.

In another aspect, a method of depositing a film selected from a carbon-doped silicon oxide film and a carbon-doped silicon oxynitride film on at least one surface of a substrate, comprising: disposing the substrate in a reactor; heating the reactor to one or more temperatures in the range of about 25° C. to about 550° C.; introducing into the reactor a combination comprising (a) 1,1,3,3-tetrachloro-1,3-disilacyclobutane as a precursor; and (b) mesitylene; introducing into the reactor a nitrogen source to react with at least a portion of the precursor to form the carbon-doped silicon nitride film; And a method of depositing a film selected from a carbon-doped silicon oxide film and a carbon-doped silicon oxynitride film on at least one surface of a substrate is provided, comprising treating the carbon-doped silicon nitride film with an oxygen source at one or more temperatures in the range of from about 25° C. to 1000° C. or from about 100° C. to 400° C. under conditions sufficient to convert the carbon-doped silicon nitride film to a carbon-doped silicon oxide film or a carbon-doped silicon oxynitride film. In certain embodiments, the carbon-doped silicon oxide film or the carbon-doped silicon oxynitride film has a carbon content of at least about 10 atomic percent (at. %) as measured by XPS and has an etch rate that is at most 0.5 times the etch rate of thermal silicon oxide as measured in diluted hydrofluoric acid. If desired, the present invention further comprises treating the carbon-doped silicon-containing film with hydrogen or a hydrogen/inert plasma at 25° C. to 600° C.

In certain embodiments, the silicon-containing film comprises silicon and nitrogen. In these embodiments, the silicon-containing film deposited using the methods described herein is formed in the presence of a nitrogen-containing source. The nitrogen-containing source may be introduced to the reactor in the form of at least one nitrogen source and/or may be incidentally present in other precursors used in the deposition process.

Suitable nitrogen containing gases or nitrogen source gases can include, for example, ammonia, ammonia plasma, hydrazine, monoalkylhydrazines, symmetrical or asymmetrical dialkylhydrazines, organic amines such as methylamine, ethylamine, ethylenediamine, ethanolamine, piperazine, N,N'-dimethylethylenediamine, imidazolidine, cyclotrimethylenetriamine, and combinations thereof.

In another aspect, a method of forming a carbon-doped silicon nitride film having a carbon content in the range of 15 at. % to 30 at. % via a thermal ALD process, comprising the steps of: a) disposing one or more substrates comprising surface features into a reactor; b) heating the reactor to one or more temperatures in the range of ambient temperature to about 550° C. and optionally maintaining the reactor at a pressure of less than or equal to 100 torr; c) introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene into the reactor; d) purging with an inert gas; e) providing a nitrogen source to the reactor to react with the 1,1,3,3-tetrachloro-1,3-disilacyclobutane to form the carbon-doped silicon nitride film; f) purging with an inert gas to remove reaction byproducts; g) repeating steps c through f to provide a desired thickness of the carbon-doped silicon nitride film. h) treating the formed carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from about ambient temperature to about 1000° C. or from about 100° C. to about 400° C. to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film; and providing a post-deposition step of exposing the carbon-doped silicon oxide film to a plasma comprising hydrogen. A method is provided for forming a carbon-doped silicon oxide film having a carbon content in the range of 15 at. % to 30 at. % by a thermal ALD process.

In another embodiment, a method of forming a carbon-doped silicon oxide film having a carbon content in the range of 15 at. % to 30 at. % via a thermal ALD process, comprising: a) disposing one or more substrates comprising surface features in a reactor; b) heating the reactor to one or more temperatures in the range of ambient temperature to about 150° C. and optionally maintaining the reactor at a pressure of less than or equal to 100 torr; c) introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane, mesitylene, and a catalyst into the reactor; d) purging with an inert gas; e) providing water vapor to the reactor to react with the 1,1,3,3-tetrachloro-1,3-disilacyclobutane in the presence of the catalyst to form a film immediately following the carbon-doped silicon oxide deposition; And f) a step of purging with an inert gas to remove reaction by-products, and repeating steps c) to f) to provide a desired thickness of the carbon-doped silicon oxide film. A method for forming a carbon-doped silicon oxide film having a carbon content in the range of 15 at. % to 30 at. % is provided through a thermal ALD process.

In one embodiment of the method described herein, a carbon-doped silicon oxide film having a carbon content in the range of 5 at. % to 20 at. % is deposited using a thermal ALD process and a plasma comprising hydrogen to improve film properties. In this embodiment, the method

a. A step of placing one or more substrates including surface features into a reactor;

b. heating the reactor to one or more temperatures ranging from ambient temperature to about 550°C and optionally maintaining the reactor at a pressure of less than 100 torr;

c. A step of introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene as a silicon precursor into a reactor;

d. A step of removing unreacted silicon precursor by purging with an inert gas and forming a composition comprising the purge gas and the silicon precursor;

e. A step of forming a carbon-doped silicon nitride film by providing a nitrogen source to the reactor and reacting with a nitrogen precursor;

f. A step of removing reaction by-products by purging with an inert gas;

g. Repeating steps c to f to provide a desired thickness of the carbon-doped silicon nitride film;

h. a step of post-deposition, wherein the carbon-doped silicon nitride film is treated with an oxygen source at one or more temperatures ranging from about ambient temperature to 1000° C. or from about 100° C. to 400° C. to convert the carbon-doped silicon nitride film to a carbon-doped silicon oxide film, either in situ or in another chamber; and

i. a step of exposing a carbon-doped silicon oxide film to a plasma containing hydrogen to provide a post-deposition that improves at least one of the properties of the film;

j. Optionally, a post-deposition step of treating a carbon-doped silicon oxide film with spike annealing at a temperature of 400 to 1000°C or with a UV light source.

In this or other embodiments, the UV exposure step may be performed during film deposition, or may be performed after deposition is complete.

In one embodiment, the substrate comprises at least one feature, the feature comprising a patterned trench having an aspect ratio of 1:9 and an opening of 180 nm.

In another embodiment, a method of improving film properties by depositing a carbon-doped silicon oxide film having a carbon content in the range of 5 at. % to 20 at. % using a thermal ALD process and a plasma comprising hydrogen is disclosed. In this embodiment, the method

a. A step of placing one or more substrates including surface features into a reactor;

b. heating the reactor to one or more temperatures ranging from ambient temperature to about 550°C and optionally maintaining the reactor at a pressure of less than 100 torr;

c. introducing into the reactor a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and a solvent selected from the group consisting of mesitylene, 2-methyl-nonane, 1,2,4,5-tetramethylpiperazine, ethoxy-benzene, and 1-ethyl-4-methyl-benzene;

d. A step of removing unreacted silicon precursor by purging with an inert gas and forming a composition comprising the purge gas and the silicon precursor;

e. A step of forming a carbon-doped silicon film by providing a nitrogen source to the reactor to react with the surface;

f. A step of removing reaction by-products by purging with an inert gas;

g. Repeating steps c to f to provide a desired thickness of the carbon-doped silicon nitride film;

h. a step of post-deposition, wherein the carbon-doped silicon nitride film is treated with an oxygen source at one or more temperatures ranging from about ambient temperature to 1000° C. or from about 100° C. to 400° C. to convert the carbon-doped silicon nitride film to a carbon-doped silicon oxide film, either in situ or in another chamber; and

i. a step of exposing a carbon-doped silicon oxide film to a plasma containing hydrogen to provide a post-deposition that improves at least one of the properties of the film; and

j. Optionally, a post-deposition step of treating a carbon-doped silicon oxide film with spike annealing at a temperature of 400 to 1000°C or with a UV light source.

In this or other embodiments, the UV exposure step may be performed during film deposition, or may be performed after deposition is complete.

In an embodiment of the method described herein, a carbon-doped silicon oxide film having a carbon content in the range of 15 at. % to 30 at. % is deposited using a thermal ALD process and a plasma comprising hydrogen to improve film properties. In this embodiment, the method

a. placing one or more substrates including surface features into a reactor (e.g., a conventional ALD reactor);

b. heating the reactor to one or more temperatures ranging from ambient temperature to about 550°C and optionally maintaining the reactor at a pressure of less than 100 torr;

c. A step of introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene into a reactor;

d. Step of purging with inert gas;

e. A step of providing a nitrogen source to the reactor to react with 1,1,3,3-tetrachloro-1,3-disilacyclobutane to form a carbon-doped silicon nitride film;

f. A step of removing reaction by-products by purging with an inert gas;

g. Repeating steps c to f to provide a desired thickness of the carbon-doped silicon nitride film;

h. a step of post-deposition, in situ or in another chamber, of converting the carbon-doped silicon nitride film into a carbon-doped silicon oxide film by treating the carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from about ambient temperature to 1000° C. or from about 100° C. to 400° C.;

i. a step of exposing a carbon-doped silicon oxide film to a plasma containing hydrogen to provide a post-deposition that improves at least one of the physical properties of the film; and

j. Optionally, a post-deposition step of thermal annealing the carbon-doped silicon oxide film at a temperature of 400 to 1000°C or treating it with a UV light source.

Includes.

In this or other embodiments, the UV exposure step can be performed during film deposition, or after deposition is complete.

In another further embodiment of the method described herein, the silicon-containing film is deposited using a thermal ALD process using a catalyst comprising ammonia or an organic amine. In this embodiment, the method comprises:

a. A step of placing one or more substrates including surface features into a reactor;

b. heating the reactor to one or more temperatures ranging from ambient temperature to about 150°C and optionally maintaining the reactor at a pressure of less than 100 torr;

c. A step of introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane, mesitylene, and a catalyst into a reactor;

d. Step of purging with inert gas;

e. A step of forming a film immediately after carbon-doped silicon oxide deposition by providing water vapor to a reactor to react with 1,1,3,3-tetrachloro-1,3-disilacyclobutane in the presence of a catalyst;

f. A step of removing reaction by-products by purging with an inert gas;

g. Repeating steps c to f to provide a desired thickness of the carbon-doped silicon oxide film;

h. a step of exposing the film to a plasma containing hydrogen to provide a post-deposition that improves at least one of the properties of the film; and

i. Post-deposition step of optionally treating a carbon-doped silicon oxide film with spike annealing at a temperature of 400 to 1000°C or with a UV light source.

In this or other embodiments, the UV exposure step may be performed during film deposition, or may be performed after deposition is complete.

In this or other embodiments, the catalyst is selected from a Lewis base such as pyridine, piperazine, ammonia, triethylamine or other organic amines. The amount of Lewis base vapor is at least 1 equivalent to the amount of silicon precursor vapor during step c.

In certain embodiments, the resulting carbon-doped silicon oxide film is exposed to an organoaminosilane or chlorosilane having Si-Me or Si-H or both prior to exposure to hydrogen plasma treatment to form a hydrophobic thin film. Suitable organoaminosilanes are diethylaminotrimethylsilane, dimethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, t-butylaminotrimethylsilane, iso-propylaminotrimethylsilane, di-isopropylaminotrimethylsilane, pyrrolidinotrimethylsilane, diethylaminodimethylsilane, dimethylaminodimethylsilane, ethylmethylaminodimethylsilane, t-butylaminodimethylsilane, iso-propylaminodimethylsilane, di-isopropylaminodimethylsilane, pyrrolidinodimethylsilane, bis(diethylamino)dimethylsilane, bis(dimethylamino)dimethylsilane, bis(ethylmethylamino)dimethylsilane, bis(di-isopropylamino)dimethylsilane, bis(iso-propylamino)dimethylsilane, bis(tert-butylamino)dimethylsilane, dipyrrolidinodimethylsilane, bis(diethylamino)diethylsilane, Bis(diethylamino)methylvinylsilane, bis(dimethylamino)methylvinylsilane, bis(ethylmethylamino)methylvinylsilane, bis(di-isopropylamino)methylvinylsilane, bis(iso-propylamino)methylvinylsilane, bis(tert-butylamino)methylvinylsilane, dipyrrolidinomethylvinylsilane, 2,6-dimethylpiperidinomethylsilane, 2,6-dimethylpiperidinodimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, tris(dimethylamino)phenylsilane, tris(dimethylamino)methylsilane, di-iso-propylaminosilane, di-sec-butylaminosilane, chlorodimethylsilane, chlorotrimethylsilane, dichloromethylsilane, and dichlorodimethylsilane.

In another embodiment, the formed carbon-doped silicon oxide film is exposed to an alkoxysilane or a cyclic alkoxysilane having Si-Me or Si-H or both prior to exposure to the hydrogen plasma treatment to form a hydrophobic thin film. Suitable alkoxysilanes or cyclic alkoxysilanes include, but are not limited to, diethoxymethylsilane, dimethoxymethylsilane, diethoxydimethylsilane, dimethoxydimethylsilane, 2,4,6,8-tetramethylcyclotetrasiloxane, or octamethylcyclotetrasiloxane. Without wishing to be bound by any theory or explanation, it is believed that the thin film formed by the organoaminosilane or the alkoxysilane or the cyclic alkoxysilane is converted to a dense carbon-doped silicon oxide during the plasma ashing process, which may further increase the ashing resistance.

In another embodiment, a vessel is provided for depositing a silicon-containing film comprising one or more silicon precursor compounds described herein. In one particular embodiment, the vessel comprises at least one pressurizable vessel (preferably made of stainless steel having a design as disclosed in U.S. Pat. Nos. US7334595; US6077356; US5069244; and US5465766, the disclosures of which are herein incorporated by reference). The vessel may comprise glass (borosilicate or quartz glass) or type 316, 316L, 304 or 304L stainless steel alloy (UNS designations S31600, S31603, S30400 S30403) equipped with suitable valves and fittings to enable delivery of one or more precursors to the reactor for a CVD or ALD process. In this or other embodiments, the silicon precursor is provided in a pressurizable vessel comprised of stainless steel, wherein the precursor has a purity of at least 98% or at least 99.5% by weight, which is suitable for semiconductor applications. The silicon precursor compound is preferably substantially free of metal ions, such as Al ³⁺ ions, Fe ²⁺ , Fe ³⁺ , Ni ²⁺ , Cr ³⁺ . As used herein, the term "substantially free" means less than about 5 ppm (by weight) of Al ³⁺ ions, Fe ²⁺ , Fe ³⁺ , Ni ²⁺ , Cr ^{3+ ,} preferably less than about 3 ppm, and more preferably less than about 1 ppm, and most preferably about 0.1 ppm. In certain embodiments, the vessel may have means for mixing the precursor with one or more additional precursors, if desired. In these or other embodiments, the contents of the vessel(s) may be premixed with the additional precursors. Alternatively, the silicon precursor and/or other precursors may be maintained in separate vessels, or in a single vessel having separation means for keeping the silicon precursor and other precursors separate during storage.

A silicon-containing film is deposited on at least one surface of a substrate, such as a semiconductor substrate. In the methods described herein, the substrate can be made of and/or coated with various materials known in the art, including films of silicon, such as crystalline silicon or amorphous silicon, silicon oxide, silicon nitride, amorphous carbon, silicon oxycarbide, silicon oxynitride, silicon carbide, germanium, germanium-doped silicon, boron-doped silicon, metals, such as copper, tungsten, aluminum, cobalt, nickel, tantalum, metal nitrides, such as titanium nitride, tantalum nitride, metal oxides, group III/V metals or metalloids, such as GaAs, InP, GaP and GaN, and combinations thereof. These coatings can completely coat the semiconductor substrate, can be made of multiple layers of the various materials, and can be partially etched to expose underlying layers of the materials. The surface may also have a photoresist material developed to be patterned thereon and to partially coat the substrate. In certain embodiments, the semiconductor substrate comprises at least one surface feature selected from the group consisting of pores, vias, trenches, and combinations thereof. Potential applications of the silicon-containing film include, but are not limited to, low k spacers for FinFETs or nanosheets, sacrificial hard masks for self-aligned patterning processes (e.g., SADP, SAQP, or SAOP).

The deposition process used to form the silicon-containing film or coating is a deposition process. Examples of deposition processes suitable for the methods disclosed herein include, but are not limited to, chemical vapor deposition processes or atomic layer deposition processes. As used herein, the term "chemical vapor deposition process" refers to any process in which a substrate is exposed to one or more volatile precursors that react and/or decompose on the substrate surface to produce the desired deposition. As used herein, the term "atomic layer deposition process" refers to a self-limiting (e.g., a constant amount of film material is deposited in each reaction cycle), sequential surface chemistry that deposits a film of material on a substrate of varying composition. As used herein, the term "thermal atomic layer deposition process" refers to an atomic layer deposition process at substrate temperatures ranging from room temperature to 600° C. without the use of an in situ or remote plasma. Although the precursors, reagents, and sources used herein may sometimes be described as "gaseous," it is understood that the precursors may be liquid or solid and are transported directly into the reactor by vaporization, bubbling, or sublimation, with or without an inert gas. In some cases, the vaporized precursor may be passed through a plasma generator.

In one embodiment, the silicon-containing film is deposited using an ALD process. In another embodiment, the silicon-containing film is deposited using a CCVD process. In a further embodiment, the silicon-containing film is deposited using a thermal ALD process. The term "reactor" as used herein includes, without limitation, a reaction chamber or a deposition chamber.

In certain embodiments, the methods disclosed herein prevent pre-reaction of the precursor(s) by using an ALD or CCVD method that separates the precursor(s) prior to and/or during introduction into the reactor. In this regard, a deposition technique, such as an ALD or CCVD process, is used to deposit the silicon-containing film. In one embodiment, the film is deposited via an ALD process in a conventional single wafer ALD reactor, a semi-batch ALD reactor, or a batch ALD reactor by alternately exposing the substrate surface to one or more silicon-containing precursors, an oxygen source, a nitrogen-containing source, or other precursors or reagents. Film growth proceeds by self-limiting control of the surface reactions, the pulse length of each precursor or reagent, and the deposition temperature. However, film growth ceases when the surface of the substrate becomes saturated. In another embodiment, each reactant, including a silicon precursor and a reactive gas, is exposed to the substrate by moving or rotating the substrate to different sections of the reactor, each section being separated by an inert gas curtain, i.e., a space ALD reactor or a roll-to-roll ALD reactor.

Depending on the deposition method, in certain embodiments, the silicon precursor described herein and optionally other silicon-containing precursors can be introduced into the reactor in a molar volume, or from about 0.1 to about 1000 micromoles. In this or other embodiments, the precursors can be introduced into the reactor for a period of time. In certain embodiments, the period of time is in the range of from about 0.001 to about 500 seconds.

In certain embodiments, silicon-containing films deposited using the methods described herein are formed in the presence of a catalyst together with an oxygen source, an oxygen-containing reagent or precursor, i.e., water vapor. The oxygen source may be introduced into the reactor in the form of at least one oxygen source and/or may be incidentally present in other precursors used in the deposition process. Suitable oxygen source gases include, for example, water (H ₂ O) (e.g., deionized water, purified water, distilled water, water vapor, water vapor plasma, oxygenated water, air, a composition comprising water and another organic liquid), oxygen (O ₂ ), oxygen plasma, ozone (O ₃ ), nitrogen monoxide (NO), nitrogen dioxide (NO ₂ ), carbon monoxide (CO), a plasma comprising water, a plasma comprising water and argon, hydrogen peroxide, a composition comprising hydrogen, a composition comprising hydrogen and oxygen, carbon dioxide (CO ₂ ), air, and combinations thereof. In certain embodiments, the oxygen source comprises an oxygen source gas introduced into the reactor at a flow rate ranging from about 1 to about 10,000 square centimeters (sccm) or from about 1 to about 1000 sccm. The oxygen source can be introduced for a time ranging from about 0.1 to about 100 seconds. The catalyst is selected from a Lewis base, such as pyridine, piperazine, trimethylamine, tert-butylamine, diethylamine, trimethylamine, ethylenediamine, ammonia, or other organic amines.

In embodiments where the film is deposited by an ALD or cyclic CVD process, the precursor pulse can have a pulse duration greater than 0.01 second, the oxygen source can have a pulse duration less than 0.01 second, and the water pulse duration can have a pulse duration less than 0.01 second.

In certain embodiments, the oxygen source is continuously flowed into the reactor while the precursor pulse and plasma are introduced sequentially. The precursor pulse can have a pulse duration greater than 0.01 seconds, and the plasma duration can range from 0.01 seconds to 100 seconds.

In certain embodiments, the silicon-containing film comprises silicon and nitrogen. In these embodiments, the silicon-containing film deposited using the methods described herein is formed in the presence of a nitrogen-containing source. The nitrogen-containing source may be introduced to the reactor in the form of at least one nitrogen source and/or may be incidentally present in other precursors used in the deposition process.

Suitable nitrogen-containing gases or nitrogen source gases can include, for example, ammonia, hydrazine, monoalkylhydrazines, symmetrical or unsymmetrical dialkylhydrazines, organic amines such as methylamine, ethylamine, ethylenediamine, ethanolamine, piperazine, N,N'-dimethylethylenediamine, imidazolidine, cyclotrimethylenetriamine, and combinations thereof.

In certain embodiments, the nitrogen source is introduced to the reactor at a flow rate ranging from about 1 to about 10,000 square centimeters (sccm) or from about 1 to about 1000 sccm. The nitrogen containing source can be introduced for a time ranging from about 0.1 to about 100 seconds. In embodiments where the film is deposited by an ALD or cyclic CVD process utilizing both nitrogen and oxygen sources, the precursor pulses can have a pulse duration greater than 0.01 seconds, the nitrogen source can have a pulse duration less than 0.01 seconds, and the water pulse duration can have a pulse duration less than 0.01 seconds. In another embodiment, the purge duration between pulses can be as short as 0 seconds or can be pulsed continuously without purge between pulses.

The deposition methods disclosed herein may involve one or more purge gases. The purge gas used to purge away unconsumed reactants and/or reaction byproducts is an inert gas that does not react with the precursor. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N ₂ ), helium (He), neon, hydrogen (H ₂ ), and combinations thereof. In certain embodiments, a purge gas, such as Ar, is supplied to the reactor at a flow rate in the range of about 10 to about 10000 sccm for a time period of about 0.1 to 1000 seconds to purge unreacted materials and any byproducts that may remain in the reactor.

Each step of supplying the precursor, the oxygen source, the nitrogen-containing source, and/or other precursor, source gases, and/or reagents can be performed by changing the time at which they are supplied, thereby changing the stoichiometric composition of the resulting film.

Energy is applied to at least one of the precursor, the nitrogen-containing source, the reducing agent, the other precursor, or a combination thereof to induce a reaction and form a film or coating on the substrate. Such energy can be provided by, without limitation, heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, x-ray, electron beam, photons, remote plasma methods, and combinations thereof.

In certain embodiments, a second RF frequency source can be used to modify the plasma characteristics of the substrate surface. In embodiments where the deposition involves plasma, the plasma generation process can include a direct plasma generation process, where the plasma is generated directly in the reactor, or alternatively, a remote plasma generation process, where the plasma is generated external to the reactor and supplied to the reactor.

Throughout the description, the term "ALD or ALD-like" refers to processes including, but not limited to: a) introducing each reactant, including a silicon precursor and a reactive gas, sequentially into a reactor, such as a single wafer ALD reactor, a semi-batch ALD reactor, or a batch ALD reactor; b) exposing the substrate to each reactant, including a silicon precursor and a reactive gas, by moving or rotating the substrate to different sections of the reactor, and separating each section by an inert gas curtain, i.e., a space ALD reactor or a roll-to-roll ALD reactor.

The silicon precursors and/or other silicon-containing precursors can be delivered to a reaction chamber, such as a CVD or ALD reactor, in a variety of ways. In one embodiment, a liquid delivery system can be utilized. In an alternative embodiment, a combined liquid delivery and flash vaporization process device, such as a turbo evaporator manufactured by MSP Corporation of Shoreview, Minn., can be used to deliver low volatility materials in a volumetric manner, resulting in reproducible transport and deposition without thermal decomposition of the precursors. In the liquid delivery formulations, the precursors described herein can be delivered in pure liquid form, or alternatively, can be employed in a solvent formulation or composition comprising them. Thus, in certain embodiments, the precursor formulations can include solvent component(s) having suitable properties that may be desirable and advantageous for a given end-use application for forming a film on a substrate.

In this or other embodiments, it is understood that the steps of the methods described herein can be performed in various orders, can be performed sequentially or simultaneously (e.g., during at least a portion of another step), and can be performed in any combination thereof. Each step of supplying the precursor and nitrogen-containing source gases can be performed by varying the duration of supplying them, thereby changing the stoichiometric composition of the resulting silicon-containing film.

In yet further embodiments of the methods described herein, the film or the immediately post-deposited film is subjected to a treatment step. The treatment step can be performed during at least a portion of the deposition step, after the deposition step, and combinations thereof. Exemplary treatment steps include, but are not limited to, treatment via high temperature thermal annealing; plasma treatment; ultraviolet (UV) light treatment; laser treatment; electron beam treatment, and combinations thereof, that affect one or more properties of the film. Films deposited with silicon precursors having one or two Si-C-Si bonds as described herein have improved properties, such as, but not limited to, a wet etch rate that is lower than the wet etch rate of the film prior to the treatment step or a density that is higher than the density prior to the treatment step, as compared to films deposited with previously disclosed silicon precursors under the same conditions. In one particular embodiment, the immediately post-deposited film is intermittently treated during the deposition process. These intermittent or inter-deposition treatments can be performed, for example, after each ALD cycle, after a specific number of ALD cycles, such as, without limitation, one (1) ALD cycle, two (2) ALD cycles, five (5) ALD cycles, or after every ten (10) ALD cycles.

In embodiments where the film is subjected to a high temperature annealing step, the annealing temperature is at least 100° C. or greater than the deposition temperature. In this or other embodiments, the annealing temperature is in the range of about 400° C. to about 1000° C. In this or other embodiments, the annealing process can be performed in a vacuum (<760 Torr), an inert environment, or an oxygen containing environment (e.g., H ₂ O, N ₂ O, NO ₂ or O ₂ ).

In embodiments where the film is treated with UV treatment, the film is exposed to a broadband UV or, alternatively, a UV source having a wavelength in the range of from about 150 nanometers (nm) to about 400 nm. In one particular embodiment, the film, immediately after deposition, is exposed to UV in a chamber different from the deposition chamber after the desired film thickness is achieved.

In embodiments where the film is treated with plasma, a passivation layer, such as SiO ₂ or carbon-doped SiO ₂ , is deposited to prevent chlorine and nitrogen contamination from penetrating the film during subsequent plasma treatment. The passivation layer can be deposited using atomic layer deposition or cyclic chemical vapor deposition.

In embodiments where the film is treated with plasma, the plasma source is selected from the group consisting of hydrogen plasma, plasma comprising hydrogen and helium, plasma comprising hydrogen and argon. Hydrogen plasma lowers the film dielectric constant and increases damage resistance due to plasma ashing process while still maintaining the carbon content in the bulk substantially unchanged.

Throughout the description, the term "ALD or ALD-like" refers to processes including, but not limited to: a) introducing each reactant, including a silicon precursor and a reactive gas, sequentially into a reactor, such as a single wafer ALD reactor, a semi-batch ALD reactor, or a batch ALD reactor; b) exposing the substrate to each reactant, including a silicon precursor and a reactive gas, by moving or rotating the substrate to different sections of the reactor, and separating each section by an inert gas curtain, i.e., a space ALD reactor or a roll-to-roll ALD reactor.

Throughout the description, the term "ashing" refers to a process of removing photoresist or carbon hard masks in semiconductor manufacturing processes using a plasma including an oxygen source, such as an O ₂ /inert gas plasma, O ₂ plasma, CO ₂ plasma, CO plasma, H ₂ /O ₂ plasma, or a combination thereof.

Throughout the description, the term "damage resistance" refers to the film properties after the oxygen ashing process. Good or high damage resistance is defined as the following film properties after oxygen ashing: the film dielectric constant is less than 4.5; the carbon content in the bulk (greater than 50 Å deep into the film) prior to ashing is within 5 at. % as before ashing; and the observed difference in diluted HF etch rate between the film near the surface (greater than 50 Å deep) and the bulk (greater than 50 Å deep) is such that less than 50 Å of the film is damaged.

Throughout the description, the term "alkyl hydrocarbon" refers to linear or branched C ₁ to C ₂₀ hydrocarbons, cyclic C ₆ to C ₂₀ hydrocarbons. Exemplary hydrocarbons include, but are not limited to, heptane, octane, nonane, decane, dodecane, cyclooctane, cyclononane, and cyclodecane.

Throughout the description, the term "aromatic hydrocarbon" refers to a C ₆ to C ₂₀ aromatic hydrocarbon. Exemplary aromatic hydrocarbons include, but are not limited to, toluene, and mesitylene.

Throughout the description, the term "catalyst" refers to a gaseous Lewis base capable of catalyzing a surface reaction between hydroxyl groups and Si-Cl bonds during a thermal ALD process. Exemplary catalysts include, but are not limited to, at least one cyclic amine-based gas, such as aminopyridine, picoline, lutidine, piperazine, piperidine, pyridine or the organic amine-based gases methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, iso-propylamine, di-propylamine, di-iso-propylamine, and tert-butylamine.

Throughout the description, the term "organic amine" refers to primary amines, secondary amines, and tertiary amines having C ₁ to C ₂₀ hydrocarbons, cyclic C ₆ to C ₂₀ hydrocarbons. Exemplary organic amines include, but are not limited to, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, iso-propylamine, di-propylamine, di-iso-propylamine, and tert-butylamine.

Throughout the description, the term "siloxane" refers to a linear, branched, or cyclic liquid compound having at least one Si-O-Si bond and C ₄ to C ₂₀ carbon atoms. Exemplary siloxanes include, but are not limited to, tetramethyldisiloxane, hexamethyldisiloxane (HMDSO), 1,1,1,3,3,5,5,5-octamethyltrisiloxane, and octamethylcyclotetrasiloxane (OMCTS).

Throughout the description, when the term "an etch rate up to x times the etch rate of thermal silicon oxide" is used, the value x is calculated by dividing the etch rate of the corresponding silicon-containing film in 1:99 diluted HF by the etch rate of thermal silicon oxide in 1:99 diluted HF (e.g., 0.45 Å/s), wherein both etch rates are measured under identical conditions.

Throughout the description, the term "step coverage" as used herein is defined as the percentage of two thicknesses of a film deposited on a structured or characterized substrate having a via or a trench or both, where the bottom step coverage is the ratio (in percent) of the thickness at the bottom of the feature divided by the thickness at the top of the feature, and the middle step coverage is the ratio (in percent) of the thickness on the sidewall of the feature divided by the thickness at the top of the feature. Films deposited using the methods described herein exhibit a step coverage of greater than or equal to about 80 percent, or greater than or equal to about 90 percent, indicating that the film is conformal.

The following examples illustrate specific embodiments of the invention and do not limit the scope of the appended claims.

Example

Example 1. Blended product comprising 20 wt% of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene

A blend was prepared by dissolving 20 wt% of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene. Figure 1 shows an overlay of the vapor pressure curves of 1,1,3,3-tetrachloro-1,3-disilacyclobutane with mesitylene, demonstrating their similarity over the temperature range of interest.

Figure 2 shows the normalized concentrations of constituent metals of common stainless steels, such as Fe, Cr, Ni and Mn, in a 20 wt % solution of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene aged for a period of time equivalent to 2 years at room temperature in stainless steel containers. The fact that these common stainless steel metals do not systematically increase over time strongly supports the compatibility of the compounded product with low moisture mesitylene components with stainless steel containers.

Figure 3 shows the normalized concentration of the chlorosilane component, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, as a function of the volume percent remaining in the vessel as it is depleted during the vapor withdrawal transfer process.

Concentration consistency was performed by depositing silicon-containing films using a 20 wt % solution of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene and ammonia in thermal ALD mode. The vessel consisted of 200 g of material in a 500 ml stainless steel vessel. The vessel was heated to 80 °C and the chemicals were delivered using vapor extraction. Film deposition was performed in a laboratory-scale atomic layer deposition (ALD) reactor using ammonia as the silicon precursor and nitrogen source. The ALD step and process conditions are given in Table 3 below:

During deposition, steps 3 to 10 were repeated for several cycles to obtain the desired thickness of the carbon-doped silicon nitride immediately after deposition.

Gas chromatography analysis was performed occasionally between runs to check the solution concentration.

As shown in Fig. 4, the film growth was consistent with GPC of 0.39 Å/cycle ± 0.03 Å/cycle. GC analyses were performed in the vessel between depositions. Tables 4 and 5 show analyses performed at intervals during the deposition while heating the solution vessel at temperatures of 80 and 70°C, respectively. As shown in the tables, the precursor concentration was constant throughout the deposition in both cases.

While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the specific embodiments disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (20)

A composition for depositing a silicon-containing film,
(a) 1,1,3,3-tetrachloro-1,3-disilacyclobutane; and
(b) Mesitylene
A composition for depositing a silicon-containing film, comprising: A composition comprising less than 5 ppm of at least one metal ion selected from the group consisting of Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Ni ²⁺ , and Cr ³⁺ in the first aspect. A method for forming a carbon-doped silicon oxide film through a thermal ALD process,
a) placing one or more substrates, each substrate comprising a surface including surface features, in a reactor;
b) heating the reactor to one or more temperatures ranging from ambient temperature to about 550°C and optionally maintaining the reactor at a pressure of less than 100 torr;
c) a step of introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene into a reactor to form a film on a surface;
d) a step of purging the reactor using an inert gas;
e) a step of forming a carbon-doped silicon nitride film by introducing a nitrogen source into the reactor and reacting with the film;
f) a step of removing reaction by-products by purging the reactor using an inert gas;
g) repeating steps c to f to provide a desired thickness of the carbon-doped silicon nitride film;
h) treating the formed carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from about ambient temperature to about 1000° C. to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film; and
i) a step of exposing a carbon-doped silicon oxide film to a plasma containing hydrogen;
A method for forming a carbon-doped silicon oxide film through a thermal ALD process, comprising: A film formed according to the method of claim 3, having a k of less than about 4 and a carbon content of at least about 10 at. %. A film formed by the method of claim 3, having an etching rate that is at most 0.5 times the etching rate of thermal silicon oxide in 1:99 diluted HF. In the fifth paragraph, the film has an etching rate of at most 0.1 of the etching rate of thermal silicon oxide. In the fifth paragraph, a film having an etching rate that is at most 0.05 times the etching rate of thermal silicon oxide. In the fifth paragraph, a film having an etching rate that is at most 0.01 times the etching rate of thermal silicon oxide. A film having a damaged layer of 50 Å or less after exposing the film to an oxygen ashing process formed according to the method of claim 3. In claim 9, a film having a damaged layer of 20 Å or less after exposing the film to an oxygen ashing process. In claim 9, a film having a damaged layer of 10 Å or less after exposing the film to an oxygen ashing process. In claim 9, a film having a damaged layer of 5 Å or less after exposing the film to an oxygen ashing process. A stainless steel container containing the composition of claim 1 or 2. A method for forming a carbon-doped silicon oxide film having a carbon content in the range of 15 at.% to 30 at.% through a thermal ALD process,
a. A step of placing one or more substrates including surface features into a reactor;
b. heating the reactor to one or more temperatures ranging from ambient temperature to about 150°C and optionally maintaining the reactor at a pressure of less than 100 torr;
c. A step of introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane, mesitylene, and a catalyst into a reactor;
d. The step of purging the reactor with an inert gas;
e. a step of forming a carbon-doped silicon oxide film by providing water vapor to a reactor and reacting it with 1,1,3,3-tetrachloro-1,3-disilacyclobutane in the presence of a catalyst; and
f. A step of purging the reactor with an inert gas to remove any reaction by-products.
A method for forming a carbon-doped silicon oxide film having a carbon content in the range of 15 at. % to 30 at. % by a thermal ALD process, comprising: providing a desired thickness of the carbon-doped silicon oxide film by repeating steps c to f. A method according to claim 14, further comprising the step of treating the carbon-doped silicon oxide film by thermal annealing at a temperature of 300 to 700°C. A method according to claim 14, further comprising the step of treating a carbon-doped silicon oxide film with a hydrogen plasma containing hydrogen. A method in claim 3, wherein the composition is introduced into the reactor through steam extraction or bubbling. A method according to claim 14, wherein the composition is introduced into the reactor through steam extraction or bubbling. A method for depositing a carbon-doped silicon oxide film having a carbon content in the range of 5 at. % to 20 at. % using a thermal ALD process and a plasma containing hydrogen,
a. A step of placing one or more substrates including a surface in a reactor;
a. Heating the reactor to one or more temperatures ranging from ambient temperature to about 550°C and optionally maintaining the reactor at a pressure of less than 100 torr;
b. a step of introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and a solvent selected from the group consisting of mesitylene, 2-methyl-nonane, 1,2,4,5-tetramethylpiperazine, ethoxy-benzene, and 1-ethyl-4-methyl-benzene into a reactor to form a film on a surface;
c. a step of purging the reactor with an inert gas to remove any unreacted composition;
d. A step of forming a carbon-doped silicon nitride film by introducing a nitrogen source into the reactor and reacting with the film;
e. A step of purging the reactor with an inert gas to remove any reaction by-products;
f. Repeating steps b to e to provide a desired thickness of the carbon-doped silicon nitride film;
g. a step of treating the carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from about ambient temperature to 1000° C. to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film in situ or in another chamber; and
h. exposing a carbon-doped silicon oxide film to a plasma containing hydrogen; and
i. A step of optionally treating a carbon-doped silicon oxide film by spike annealing at a temperature of 400 to 1000°C or with a UV light source.
A method for depositing a carbon-doped silicon oxide film having a carbon content in the range of 5 at. % to 20 at. % using a thermal ALD process including a plasma containing hydrogen. A composition for depositing a silicon-containing film,
(a) 1,1,3,3-tetrachloro-1,3-disilacyclobutane; and
(b) a solvent selected from the group consisting of mesitylene, 2-methyl-nonane, 1,2,4,5-tetramethylpiperazine, ethoxy-benzene, and 1-ethyl-4-methyl-benzene;
A composition for depositing a silicon-containing film, comprising: